Dehydrogenation

ABSTRACT

Dehydrogenation process using an improved catalyst formed from a phosphorus-containing material such as phosphoric acid, a tin material such as tin chloride, and one of a Group Ia or IIa metal or metal-containing material.

United States Patent Nolan et a]. Jan. 29, 1974 DEHYDROGENATION [56]References Cited [75] Inventors: George J. Nolan, Tahlequah; RobertUNITED STATES PATENTS J- og Bartlesville, both of Qkla- 3,513,215 5/1970Ogle 260/680 3,274,283 9/1966 Bethell 260/680 [73] Assgnee' g lif gi3,320,329 5/1967 Nolan 260/680 e, 3,501,54s 3/1970 Nolan 6:61. 260/680[22 i 2 1971 3,501,547 3/1970 Nolan et al. 260/680 [2]] Appl 175398Primary Examiner-Paul M. Coughlan, Jr.

Related US. Application 0 1 Attorney, Agent, or Firm-J. Arthur Young eta1. [63] Continuation-impart of Ser. No. 810,831, March 26,

1969, abandoned, which is a continuation-in-part of [57] ABSTRACT 6543411967 abandoned Dehydrogenation process using an improved catalyst formedfrom a phosphorus-containing material such as [52] 26 2 phosphoric acid,a tin material such as tin chloride, Int Cl 5/18 and one of a Group laor Ila metal or metal-containing 5s Field of Search 260/680 E; 252/437matenal' 23 Claims, No Drawings DEHYDROGENATION This application is acontinuation-impart of a co pending application, Ser. No. 810,831, filedMar. 26, 1969, now abandoned, which was a continuation-inpart ofcopending application Ser. No. 654,341, filed July 19, 1967, nowabandoned.

This invention relates to a new and improved dehydrogenation catalystand a dehydrogenation process using the improved catalyst.

Heretofore, oxidative dehydrogenation catalysts have been formed fromphosphoric acid and tin oxide.

It has now been found that improved oxidative dehydrogenation catalystscan be formed from phosphoric acid or a phosphate as hereinafterdefined, a tin material such as a tin halide, and at least one of aGroup la or lla metal or metal-containing material as hereinafterdefined.

The Group la and lla metals are those shown in the Periodic Table in theHandbook of Chemistry and Physics, published by the Chemical RubberCompany, 45th Edition 1964), page B-2, and include lithium, sodium,potassium, rubidium, cesium, francium, beryllium, magnesium, calcium,strontium, barium, and radium. Preferred are lithium, calcium,magnesium, and barium.

The new catalysts are useful for oxidatively dehydrogenating organiccompounds such as alkenes, alkadienes, cycloalkenes, alkylpyridines, andalkyl aromatics.

The products of the process and catalysts of this invention areunsaturated compounds such as isoprene, styrene, and2-methyl-5-vinylpyridine which are useful as monomers for polymerizationprocesses to make useful materials such as rubber for pneumatic tires,polystyrene, and the like. Other products that can be produced accordingto this invention are heterocyclic compounds such as furan, furfural,methyl furan, .pyran, and the like.

Accordingly, it is an object of this invention to provide a new andimproved dehydrogenation method.

It is another object of this invention to provide a new and improvedcatalyst useful in dehydrogenation processes.

Other aspects, objects and advantages will become apparent to thoseskilled in the art upon consideration of this disclosure.

By this invention a catalyst is formed from the combination of an alkalimetal phosphate, phosphoric acid and/or a phosphate as hereinafterdefined, at least one tin compound as hereinafter defined, and at leastone of a Group la or Ila metal-containing compound as hereinafterdefined, each combined with the other in amounts that form a finalcomposition effective as a catalyst for the oxidative dehydrogenation ofmaterials specified hereinafter.

" Sub stan tially any phosphorus, tin, and Group la orlla containingmaterials can be employed in the catalyst so long as at least one of thematerials used contains oxygen, none of the materials is deleterious todehydrogenation catalytic effects, and all the elements in the materialsused other than phosphorus, tin, oxygen, and

Group la or lla are volatilized by heating the catalyst to at least thetemperature at which the catalyst is used, e.g., 1,000F., or are removedby washing the catalyst, e.g., with water.

Suitable phosphorus-containing materials include, besides phosphoricacid, phosphorus pentoxide, the phosphorus halides, and the Group la andlla metal phosphates such as lithium phosphate, sodium phosphate,potassium phosphate, rubidium phosphate, cesium phosphate, magnesiumphosphate, calcium phosphate, and the like. Other phosphorus-containingmaterials that can be employed in this invention are ammonium phosphateand monoand dibasic phosphates of ammonium and of Group Ia and llametals such as lithium monobasic phosphate, sodium dibasic phosphate,beryllium dibasic phosphate, magnesium dibasic phosphate, bariummonobasic phosphate, ammonium phosphate, ammonium dibasic phosphate, andthe like.

The tin materials employed include any such material soluble ordispersable in water, alcohol, or ether and include both stannous orstannic compounds. Representative examples of suitable tin compoundsare, for sake of brevity, given only as the stannic compound but it isto be understood that the corresponding stannous compound is equally asapplicable.Representative examples include stannic halides (stannicfluoride, stannic chloride, stannic bromide, stannic iodide), stannicsulfate, stannic acetate, stannic oxide, stannic tartrate, and stannicnitrate.

Besides elemental Group la or lla metals, Group la or Ilametal-containing materials that can be used include the nitrates, thehalides, the sulfates, the oxalates, the acetates, the carbonates, thepropionates, the tartrates, the bromates, the chlorates, the oxides, thehydroxides, and the like. Presently preferred are the Groupla-containing materials, preferably lithium, potassium, or sodium; andmost preferred are the lithiumcontaining materials.

The phosphorus-containing materials, the tincontaining materials, andthe Group la or lla metal or metal-containing materials can be combinedin any conventional manner which will yield catalytic combinationssuitable for conventional oxidative dehydrogenation processes. Forexample, the catalyst components can be combined using a coprecipitationtechnique as disclosed in detail hereinafter in the specific examples,by conventional aqueous or nonaqueous solution or suspension mixing, byion exchange, by simply mixing the components by themselves without theuse of additional solvents, and the like, including combinations ofthese techniques.

Generally, the catalysts can be formed by mixing the components forperiods varying from about 1 minute to 5 hours in the presence ofabsence of a solvent or dispersant, at temperatures from about roomtemperature up to about 200F. Ambient, sub-ambient, or superambientpressures, and ambient or inert atmosphere such as nitrogen, and thelike can be used.

Suitable solvents or dispersants that can be employed for the combiningof the catalyst components include water, alcohol, or ethers for thestep of combining the tin compound and phosphorus compound, and thesesolvents as well as hydrocarbons, halogenated hydrocarbons, ketones,esters, and the like for any other steps of the catalyst preparation.

The catalyst itself when finished and in a condition for use in anoxidative dehydrogenation process will contain from about 0.1 to about16 weight per cent phosphorous, from about 15 to about weight per centtin, and from about 0.1 to about 10 weight per cent Group la and/or Ilametal, preferably 0.1 to 5 weight per cent, all weight percentages beingbased upon the total weight of the final catalyst. The amounts ofphosphorus, tin, and Group la and/or lla metal present in the finalcatalyst total less than 100 per cent of the catalyst, the differencebetween the total and the 100 per cent being substantially combinedoxygen in sufficient amount to satisfy the valence requirements of theGroup la and/or lIa metal, tin, and phosphorus.

A presently preferred method of making the catalyst of this invention isto mix solutions or suspensions of, for example, the phosphates and/rphosphoric acid, one or more tin compounds, one or more Group Ia and/orIla metal or compound, and at least one of ammonia, ammonium hydroxide,sodium hydroxide and potassium hydroxide, filter, wash to remove anyundesirable electrolytes, dry, and calcine. A particleforming step suchas pelletizing or screening can precede or follow the drying step orcalcining step.

The concentration of the various solutions that can be used to make thecatalyst can vary widely, e.g., from about 0.01 to about molar or more,depending on the solubility of the particular materials employed. Anyorder of mixing can be used, and the final pH of the mixture isgenerally in the range of from about 2 to about 10, preferably fromabout 3.5 to about 6.5. As is demonstrated in Catalyst Testing VII], thecatalyst prepared at a pH of 8 or higher is substantially stronger thana catalyst prepared at a lower pH. The precipitate that forms isseparated from the liquid by any conventional means such as filtration.Thereafter the precipitate is washed with dilute aqueous ammonium saltsolutions such as ammonium acetate, ammonium nitrate, ammonium sulfate,and the like, and/or with deionized water to remove electrolytes. Thewashed precipitate is then dried for from about 2 to about 24 hours attemperatures of from about 100 to about 300F in air or an inertatmosphere such as nitrogen. The dried precipitate is then calcined fromabout 1 to about 24 hours at from about l,000 to about 1,500F,preferably at about the temperature at which the catalyst is to be usedin the dehydrogenation process, under ambient or inert atmospheres. Thedrying and calcining steps remove water and other volatile materialsfrom the catalyst, thus preshrinking the catalyst so that it will notshrink further when used in the dehydrogenation process, and also serveto activate the catalyst. As mentioned before, the particle-forming stepcan precede or follow the drying or calcining step. The dried andcalcined catalyst is preferably formed into 1 16- to Vz-inch pellets bycompression molding or extrusion, or is simply screened to a desiredsize, such as 10-28 mesh (Tyler Sieve Series, Mechanical EngineersHandbook by L. S. Marks, 4th Edition, McGraw-Hill Book Co., Inc., N. Y.,1941, P. 836). Optimally a particulate tin/phosphorus/oxygen material isformed, and the Group la and/or Ila metal-containing compound orcompounds is added by, for example, impregnation followed by presence ofsteam. The alkenes and alkadienes can contain from 3 to 10, preferably 4to 6, carbon atoms per molecule, inclusive, and the cycloalkenes cancontain from 4 to 10, preferably 4 to 6 carbon atoms per molecule,inclusive. The alkyl pyridines and alkyl aromatics can contain from 1 to4, preferably 1 to 2, alkyl groups per molecule which themselves containfrom 1 to 6, preferably 4 to 6, carbon atoms per group, inclusive, withat least one alkyl group having at least 2 carbon atoms.

Examples of suitable materials include propylene, nbutene, n-pentene,isopentenes, octenes, decenes, pentadiene, butadiene, isoprene, and thelike. Also included are alkyl-substituted and unsubstituted cycloalkenessuch as cyclobutene, cyclopentene, cyclohexene, 3-isopentylcyclopentene,and the like. Other materials include ethylbenzene, propylbenzene,n-butylbenzene, isobutylbenzene, hexylbenzene, l-methyl-2-propylbenzene, l-butyl-3-hexylbenzene, and the like. Still othermaterials include ethylpyridine, 2-methyl-5- ethylpyridine,2,3,4-trimethyl-S-ethylpyridine, 2-ethyl-5-hexylpyridine, and the like.

Preferred reactions applicable to this inventionare the formation of1,3-butadiene from butenes, 1,3-

pentadiene from pentenes, isoprene from 2- methylbutenes, styrene fromethylbenzene, and 2-methyl-5-vinylpyridine from 2-methyl-S-ethylpyridine, furan and acetaldehyde from butadiene, furfural, furan,and methyl furan from isoprene.

The catalysts of this invention can be used in the form of granules,mechanically formed pellets, or any other conventional form for acatalyst. The catalysts can also be employed with suitable supporting ordiluting materials such as alumina (preferably eta or gamma or mixturesthereof), boria, beryllia, magnesia, titania, zirconia, and similarconventional materials known in the art.

The amount of catalyst employed will vary widely depending on thematerials present and the conversion and selectivity desired, butgenerally the amount will be that which, for the given reaction, is aneffective catalytic amount to produce the desired dehydrogenationresults.

The molecular oxygen-containing gas employed can be present as such orwith inert diluents such as nitrogen and the like. Suitable molecularoxygen-containing gases include air, flue gases containing residualoxygen, and any other conventional gas of a similar nature. Pure orsubstantially pure oxygen can also be employed if desired.

The operating conditions for the process of this invention can varywidely but will generally include a temperature from about 700 to about1,300F, preferably from about 800 to about 1,200F; a pressure from about0.05 to about 250, preferably from about 0.l to

about 25, psia; an oxygen to gaseous organic compound feed volume ratioof from about 0.1/1 to about 3/l, preferably from about 0.5/1 to about2/1; and, if used, a steam to organic compound feed volume ratio of 0.11 to 50/1, preferably 5/1 to 20/1. The organic compound feed space rate(volumes organic compound vapor/volume of catalyst/hour, 32F, 15 psia)can be from about 50 to about 5,000, preferably from about to about2,500.

The process of this invention is ordinarily carried out by forming amixture, preferably preheated, of organic compound feed, steam, if used,and oxygen and/ or oxygen-containing gases and passing this mixture overthe catalyst at the desired temperature. Recycle of unconverted organiccompound feed can be employed if desired; however, the conversion ratesand selectivity of this invention are generally sufficiently high tojustify a single pass operation, if, for example, the product streamscan be used without separation steps in a subsequent operation, such aspolymerization.

EXAMPLE CATALYST PREPARATIONS Catalyst 1 Aqueous ammonia (28 weight percent NH was added with stirring to 3 liters of deionized watercontaining sufficient 85 per cent phosphoric acid and SnCl '5l-l O toyield a final phosphorus content of 3.1 weight per cent and a final tincontent of 73 weight per cent, both weight percentages being based onthe total weight of the catalyst. Sufficient ammonia was added to give afinal pH of 4, and the product was filtered, washed twice with 3-literportions of 0.5 molar NH NO once with a 3-liter portion of deionizedwater, and dried 58 hours at 240F. and 2 hours at 1,100F.

Catalyst 2 A. 46.5 pounds (lb) of SnCl '5l-l O was dissolved in 13liters (l) of deionized water.

B. 8 gallons (gal) of aqueous ammonia (28 weight per cent Nl-l wasdiluted with 8 gal of deionized water.

A and B were added to 13 gal of deionized water over a 27-minute periodwith stirring, with the addition rate of B controlled to maintain the pHof 5. About 15 gal of B was used. After 1 hour of stirring thesuspension was filtered, and the precipitate was washed 4 times with asolution of 6.5 lb NH NO in 20 gal of deionized water, and twice with asolution of 1.5 lb of NI-l NO in 20 gal of deionized water. Afterfiltration it was determined that the wet gel contained 38 weight percent SnO Catalyst 3 A paste was made of 100 grams (g) of commercialstannic oxide identified as B and A and marketed by Allied ChemicalCompany and 7.5 g of 85 per cent phosphoric acid, formed into /z-inch,diameter and height, pellets, and calcined 3 hours at 1,100F. The finalphosphorus content was 1.9 weight per cent and the final tin content was76 weight per cent, both weight percentages based on the total weight ofthe catalyst.

Catalyst 4 To a 4470 g portion of Catalyst 2, 316 g of 85 per centphosphoric acid was added with rapid stirring over a 30-minute period.The resulting material was air dried 2 days, and calcined 1 hour in airat l,lF. The temperature was increased from ambient to 1,100F. at therate of per minute. Thecalcined material was ground to about 6 mesh(Tyler). The final phosphorus content was 5.0 weight per cent and thefinal tin content was 69 weight per cent, both weight percentages basedon the total weight of the catalyst.

Catalyst 5 Sufi'icient lithium chloride to give 5 weight per centlithium in and based on the total weight of the final catalyst wasdissolved in sufficient deionized water to just wet a l5-gram portion ofCatalyst 4 and added to that amount of catalyst, mixed, dried 2 hours inair at 320F. and calcined 2 hours in air at 1,100F. Catalyst 6 Thiscatalyst was prepared in the same manner as Catalyst 5 except thatmagnesium nitrate was used. Catalyst 7 This catalyst was prepared in thesame manner as Catalyst 5 except that barium nitrate was used. Catalyst8 This catalyst was prepared in the same manner as Catalyst 2. After thefinal filtration it was determined that the wet gel contained 25 weightper cent SnO Catalyst 9 A paste was made by mixing 30 milliliters (ml)of deionized water, 2.5 g of lithium nitrate, 1.86 g of 85 per centphosphoric acid, and 50 g of commercial stannic oxide identified as Band A and marketed by Allied Chemical Company, dried 24 hours in avacuum oven at l94F., and calcined 2 hours at 1,100F. The lithium,phosphorus, and tin contents were 0.5, 0.9, and 76 weight per cent,respectively, based on the total weight of the catalyst.

Catalyst 10 A paste was made by mixing 25 ml of deionized water, 5 g oflithium nitrate, 14.9 g of 85 per cent phosphoric acid, and 208 g ofCatalyst 8 (equivalent to 50 g of SnO dried 24 hours in a vacuum oven at320F., and calcined 2 hours at 1,100F. The lithium, phosphorus, and tincontents were 1.3, 6.6, and 63 weight per cent, respectively, based onthe total weight of the catalyst.

Catalyst 11 This catalyst was prepared in the same manner as Catalyst 10except that 15 g of lithium nitrate was used. The lithium, phosphorus,and tin contents were 3.5, 6.6, and 60 weight per cent, respectively,based on the total weight of the catalyst.

Catalyst 12 This catalyst was prepared in thesame manner as Catalyst 10except that 9.29 g of 85 per cent phosphoric acid was used. The lithium,phosphorus, and tin contents were 1.2, 4.2, and 68 weight per cent,respectively, based on the total weight of the catalyst. Catalyst 13This catalyst was prepared in the same manner as Catalyst 12 except that0.20 g of 85 per cent phosphoric acid was used. The lithium, phosphorus,and tin contents were 2.6, 3.6, and 67 weight per cent, respectively,based on the total weight of the catalyst. Catalyst 14 This catalyst wasprepared in the same manner as- Catalyst 10 except that no lithiumnitrate was used. The phosphorus and tin contents were 7.1 and 65 weightper cent, respectively, based on total weight of the catalyst.

Catalyst 15 This catalyst was prepared in the same manner as Catalyst 12except that no lithium nitrate was used. The phosphorus and tin contentswere 4.6 and 70 weight per cent, respectively, based on the total weightof the catalyst.

Catalyst 16 This catalyst was prepared in the same manner as Catalyst 9except that the stannic oxide used was a portion of Catalyst 8 thathad'been calcined 3 hours at 1,100F., and the amounts of lithium nitrateand per cent phosphoric acid used were such that the lithium,

phosphorus, and tin contents were 0.8, 4.3, and 69 weight per cent,respectively, based on the total weight of the catalyst.

Catalyst 17 A 196 g of SnCl '5l-l O was dissolved in 1 liter ofdeionized water, and 100 ml of concentrated sulfuric acid and 24.5 g of85 phosphoric acid were added.

B. An aqueous ammonia solution containing about 8 weight per cent Nl-lwas prepared.

C. 264 g of ammonium sulfate was dissolved in sufficient deionized waterto make 1 liter.

A and B were added to C with rapid stirring over a 30-minute period. Therate of addition of B was adjusted to maintain the pH at about 5.5.After filtration the precipitate was washed twice with 3 liters of 0.5molar ammonium sulfate and once with 2 liters of deionized water. Thewet gel contained 25.2 weight per cent solids. A 198.5-g portion of thewet gel was mixed with 13.88 g of lithium nitrate dissolved in about 25ml deionized water, dried at 212F. for several hours, and calcined 2hours at 1,100F. Lithium, phosphorous, and tin contents were 2.3, 5.8,and 64 weight per cent, respectively, based on the total weight of thecatalyst. Catalyst 18 The tin-phosphorous gel used for preparing thiscatalyst was prepared in the same manner as that used for Catalyst 17except that 185 g of SnCl '5H O and 30 g of 85 per cent phosphoric acidwere used, and the addition time was 40 minutes. The wet gel contained19.6 weight per cent solids. A 235-g portion of the wet gel was mixedwith 12.81 g of lithium nitrate dissolved in about 25 ml deionizedwater, dried at 212F. for several hours, and calcined 2 hours at 1,100F.Lithium, phosphorous, and tin contents were 2.3, 7.2, and 60 weight percent, respectively, based on the total weight of the catalyst.

Catalyst 19 This catalyst was prepared by mixing 4 liters of. an aqueousammonium hydroxide solution containing 1,500 ml of ammonium hydroxide, 9liters of an aqueous solution of stannic chloride containing 4 lb ofSnCl '5H O, and 1,000 ml of an aqueous solution of phosphoric acidcontaining 335 g of 85 per cent phosphoric acid. The pH of the finalmixture was about 4.5. The precipitate formed in the final mixture wasseparated from the liquid by filtering, washed twice with 0.5-molarammonium nitrate, and finally with 16 liters of 0.1 molar ammoniumnitrate. The washed precipitate was then dried at a temperature of 300Fand ambient pressure. The dried catalyst was calcined for hours at1,100F and ambient pressure. Phosphorus and tin contents were 9.0 and 60weight per cent, respectively, based on the total weight of thecatalyst. Catalyst 20 This catalyst was prepared by adding an aqueoussolution of phosphoric acid containing 21 grams of 85 weight per centphosphoric acid and diluted to a concentration of 45 weight per centacid to an aqueous slurry of calcium hydroxide containing 20 grams ofcalcium hydroxide to give a resulting mixture which had a phosphate tocalcium weight ratio of about 2/3. To this resulting slurry was addedsufficient calcium hydroxide to give a calcium oxide to phosphoruspentoxide weight ratio of about 4.8/1. This mixture was then rapidlystirred at 80F. and a mixture of stannic chloride and phosphoric acidwas added to the stirred mixture. The mixture of stannic chloride andphosphoric acid had a stannic oxide to the dibasic stannic phosphateweight ratio of about 2.5/1. Aqueous ammonia was simultaneously added tothe stirred mixture to maintain the pH at 6. A precipitate was thusformed, separated by filtration, washed twice with 2 liters of 0.5 molarNl-LNO and once with 2 liters of 0.1 molar Nl-LNO dried for about 24hours at 320F. under ambient atmosphere and pressure, and calcined 4hours at 1,100F. under ambient atmosphere and pressure. Calcium,phosphorus, and tin contents were 7.9, 10.5, and 50 weight per cent,respectively, based on the total weight of the catalyst. Catalysts 2l25Various amounts of stannous sulfate, lithium dihydrogen phosphate, andammonium dihydrogen phosphate were dry mixed with 6 weight percentCabO-Sil (finely divided silica) and 3 percent lubricant. The mixtureswere tableted, calcined overnight at 1,200F, ground, and screened to12/28 mesh (Tyler). The lithium, phosphorous, and tin contents, based onthe total weight of the catlaysts were as follows:

Weight Percent Catalyst Li P Sn Weight Percent Catalyst Li P Sn Catalyst30 A. 17.22 pounds of SnCl -5H O and 100 milliliters of concentratedhydrochloric acid were dissolved in four gallons of deionized water.

B. 3.72 pounds of percent H PO were dissolved in two gallons ofdeionized water.

C. One pound of (Nl-l SO and 7 liters of 58 percent ammonium hydroxidewere dissolved in 15 gallons of deionized water.

The temperature of all three solutions was adjusted to about 70F.

A reactor was filled with 5 gallons of deionized water and 0.5 pound of(NH SO and the pH was adjusted to 3.5. The temperature of the reactorwas maintained at F or below.

Solutions A and B were mixed and fed to the reactor over a one-hourperiod. Solution C was fed to the reactor at the rate required tomaintain the pH at about 3.5. After one hour of stirring, the mixturewas filtered and the precipitate was washed with one pound of ammoniumsulfate in 10 gallons of deionized water. This step was repeated fourtimes. The precipitate was then spray-dried and tableted, ground, andscreened to 8/ 16 mesh (U.S.). The granules were impregnated withaqueous lithium nitrate solution, and calcined. The percentagesphosphorus, lithium, and tin, based on the total weight of the catalystswere 10, 1.5, and 58.4, respectively. Catalyst 31 A. 274 grams of SnCl-5l-l O was dissolved in liters of deionized water followed by theaddition of 118 grams of 85 per cent H PO and 175 milliliters ofapproximately 96 per cent H 50 B. 420 milliliters of concentratedammonium hydroxide was diluted with one liter of water.

Solutions A and B were added simultaneously over a period of about fiveminutes to a one-liter solution of two molar (NH SO The pH was adjustedto 4.5, the solution was filtered and the precipitate was washed oncewith 3 liters of deionized water, dried at 150C and calcined at 1,100F.

The catalyst contained 46 percent tin and 16 percent phosphorus, basedon the total weight of catalyst. Catalyst 32 This catalyst was preparedin the same manner as Catalyst 31, except that pH during a 40-minuteaddition period was kept at 5.5, the precipitate was washed twice with 3liters of 0.5 molar ammonium sulfate and once with two liters ofdeionized water, and the wet gel was impregnated with aqueous lithiumnitrate. The catalyst contained 63 percent tin, 2.3 percent lithium, and7.2 percent phosphorus, based on the total weight of catalyst.

Catalyst 33 One cc of 85 percent H PO was added to a slurry of 15 gramsof stannous sulfate and 10 cc of H 0. The

mixture was dried at 500F and calcined at 1,100F.

The catalyst contained 72 weight percent tin, 3 weight CATALYST TESTING1 All catalysts were tested for butene-2 dehydrogenation at atmosphericpressure and a furnace temperature of 1,000F., using the following gasflows:

TABLE 1 Space Rate, v/v/hr (a) Butene-2 200 Air 1000 Steam 2400 2500 (a)Space rates are expressed as volumes of vapor per volume of catalyst perhour at 32F and 15 psia.

Butene conversion (conv) and butadiene yield (yld), both in moles per100 moles of butene-2 in the feed, were determined after V4 and 3 hourson stream. Those data, which are given in Table ll, indicate that notonly are the butene conversion and-butadiene yield higher initially withthe catalysts of this invention, but, surprisingly, remained higher fora full 3 hours on stream. In an extended run made with one of thecatalysts of the invention with a somewhat higher steam space rate,which is also given in Table II, the butadiene yield decreased only 4percentage points in 238 hours. Thus, the catalysts of the inventionsurprisingly permit both a longer dehydrogenation period and a higherbutadiene yield than can be obtained by the non-promoted tin/phosphoruscatalysts.

TABLE 11 Time on Stream, hours Promoter Wt., per cent Method of H4 3Catalyst Metal WL, %(2) P Sn Preparation Conv Yld Conv Yld 1 3.1 73Copptn (sn/P) 90 77 70 17 Li 2.3 5.8 64 Copptn (Sn/P)-wet gel impreg(Li) 87 78 87 79 18 Li 2.3 7.2 Copptn (Sn/P)-wet gel impreg (Li) 97 8997 89 14 7.1 Pptn (Sn)-wet gel impreg (P) 96 82 79 62 15 4.6 Pptn(Sn)-wet gel impreg (P) 93 8O 69 58 10 Li 1.3 6.6 63 Pptn (Sn)-wet gelimpreg (Li/P) 99 84 77 66 l 1 Li 3.5 6.6 60 Pptn (Sn)-wet gel impreg(Li/P) 98 86 98 84 12 Li 1.2 4.2 68 Pptn (Sn)-wet gel impreg (Li/P) 9684 73 13 Li 2.6 3.6 67 Pptn (Sn)-wet gel impreg (Li/P) 76 92 79 3 1.9 76lmpreg of comm l SnO with P 93 84 57 42 9 Li 0.5 0.9 76 lmpreg of comm'lSnO, with Lil? 63 60 16 Li 0.8 4.3 69 impreg of calcined SnO gel withLi/P 9O 84 75 4 5.0 69 lmpreg of wet SnO gel with P 91 82 65 53 5 Li 5.05.0 69 impreg of wet SnO, gel with P, and 87 74 82 71 6 Mg 5.0 5.0 69impreg of this material after 89 76 72 59 7 Ba 5.0 5.0 69 calcining withpromoter metal 85 75 71 60 I9 9.0 60 Copptn (Sn/P) 94 86 70 54 20 Ca 7.910.5 50 Ca/Sn/P copptd in presence of 97 88 79 64 copptd Ca/P 18(1) Li2.3 7.2 60 Copptn (Sn/P)-wet gel impreg (Li) 99 93 98 89 1) Steam spacerate during this extended run was 4000 v/v/hr. There was no regenerationduring the run.

(2) Based on the total weight of the catalyst.

CATALYST rEs'riNG n Catalysts 21-25 were tested for butenedehydrogenation according to procedure of Catalyst Testing 1;

The results are given in Table 111.

The results obtained with the catalyst prepared by drymixing arecomparable with those for the catalyst prepared by the wet procedure.

CIA-TALYSTETESTING III Catalysts 26-29 were tested for butenedehydrogenation according to the procedure of Catalyst Testing 1. Thecatalysts were evaluated at 1000F, 200 GHSV butenes, 1,000 GHSV air, and2,400 GHSV steam. The results are given in Table IV.

TABLE 111 TABLE IV Time on Stream 15 min 1 hr 3 hr CatalystConversion/Yield Adding lithium as lithium dihydrogen phosphatestabilized catalyst conversion and yield over the three hour run and aresuperior to impregnation after calcining as a means of adding lithium tothe phosphoruscontaining catalysts.

CATALYST TESTING IV Catalyst 30 was tested for butene oxidativedehydrogenation according to the procedure of Catalyst Testing 1.Results are given in Table V.

Results are comparable with those for the other catalysts tested.

CATALYST TESTING V Catalysts 31 and 32 were tested according to theprocedure of Catalyst Testing 1, except that the hydrocarbon feed was1,3-butadiene instead of n-butene. The results are given in Table V1.

Conversion/Yield Butene M01 ratio to butene 1000F 1000F 900F CatalystGHSV steam air 15 min 3 hr 15 min TABLE V Conversion/Yield Butene M01ratio to butene 900F 1000F GHSV steam air 1/4 hr 3 hr l/4 hr 3 hr TABLEVI GHSV Conv. Yield of Run 1.3- of Yield of Acetalde- Temp Buda- C HFuran, hyde, F diene 0 N Steam M01,% M01,%

Catalyst 31 1100 400 200 1800 8000 2.82 0.28 0.25 1100 50 450 2000 6.311.99 0.47 1200 100 50 450 2000 11.32 2.21 0.79 1000 50 100 500 45.746.16 1.45 1000 200 400 600 4000 7.18 2.58 0.78

Catalyst 32 1000 100 100 400 2000 6.56 1.72 0.83 1100 100 100 400 200023.88 5.82 1.45 1200 100 100 400 2000 33.88 8.05 1.40 1000 50 50 2001000 24.59 4.63 1.65 1000 50 100 150 1000 29.52 5.79 1.47

VI Continued GHSV Conv. Yield of Run 1,3- of Yield of Acetalde- TempBuda- C 11, Furan, hyde,

"F diene N Steam Mol,% Mo1,%

Catalyst 32 Continued CATALYST TESTING VI pH of 4 was crushed to a finedust under a load of 500 pounds per square inch of powder surface,whereas the catalyst prepared at a pH of 8 withstood a load of 75 ,0- 00pounds per square inch of powder surface.

These results demonstrate the catalyst prepared at a pH are 8substantially stronger than the catalyst prepared at a-pI-I of 4.

Catalyst 33 was tested according to the procedure of Catalyst Testing 1.Results are given in Table VII. 2

CATALYST TESTING VII Catalyst 34 was tested according to the procedureof Catalyst Testing 1. Butene was converted at a tempera- CATALYSTTESTING IX ture of 1,000F. Results are given in Table VIII. Catalystswere prepared by slowly adding, over an in- TABLE vii GHSV Temp.,Conversion/Yield Feed feed air steam F after 15 min Z-Methyl- 200 10005000 900 73/65 butene Pentene 2 200 1000 2400 1000 97/91 TABLE VIII Iterval of about minutes, 316 parts by weight of 85 per cent phosphoricacid to 4470 parts by weight of hy- M01 Ratio to Butene drous stannicoxide containing 38 per cent solids with GHSV Cmvmbn/Yidd rapidstirring. The resulting hydrous gel was air dried 40 for two days, andthen calcined one hour in 1,000 GHSV of air at approximately 1,100F. Thecalcined material was ground to less than or equal to about 6 mesh andused as Catalyst 37 in runs shown in Tables CATALYST TESTING VIII x andXI below.

Two catalysts were prepared according to the proce- Portions of theabove-prepared /P P H- Y- dure 0f Catal st 1, exc t th t one t l t was iigen catalyst were impregnated with aqueous solutions tated at a pH of 4and the other at a pH of 8. The eat of desired metal salt promoters togive the indicated lysts were then tested according to the procedure ofpercent by weight amount of promoter.

Catalyst Testing 1. The dehydrogenation period was for The severalcatalysts then were tested under oxida- 15 minutes at a temperature of1,000F. Results are tive dehydrogenation conditions using 200 GI-ISVbugiven in Table IX.

It was also found that the catalyst precipitated at a shown in thefollowing tables: 1

" TABLE 1x Butadiene Yield pH at GHSV M01 Ratio to Butene Conv./ PerUnit Precipitation Butene steam air Yield Surface Area TABLE X Cata-Conversion Temperature |000F lyst After A Hr. After 1 Hr. After 3 Hrs.No. Catalyst Con. Mod. Con Mod. Con. Mod.

37 Control Sn/P/O 88 87 73 83 63 38 +0.2 Li 9O 87 77 64 81 39 +2.0 Li 8785 85 86 82 87 tene, 1,000 GI-ISV air, 2400 GHSV steam. Results are pCata- Conversion Temperature 1000F lyst After V Hr. After 1 Hr. After 3Hrs. No. Catalyst Con. Mod. Con. Mod. Con. Mod.

41 +2.0 Na 89 89 76 86 62 81 42 +0.2 K 91 86 79 84 68 82 43 +0.2 Rb 8688 67 82 s9 s1 44 +2.0 Rb 78 9o 69 88 57 82 TABLE X1 catalystcomposition containing weight per cent phosphorus was impregnated withvarious amounts of p w sodium nitrate solution to provide catalystscontaining Catalyst After After various amounts of sodium as indicatedin Tables Xll No. Catalyst Con. Mod. Con. Mod.

and Xlll. These catalysts then were utilized in compar 37 Control Sn/P/O85 88 87 85 ative runs with a butene-2 feed at 900F, and also 38 82 3988 85 1000F, with the results as shown being on samples 39 +2.0 L1 67 8892 82 40 +0.2 Na 82 88 92 85 taken after 3 hours operation. V 4; 2 12a:1 3 31 3; These data indicate the high effectiveness of our so- 4 43+02 Rb 83 88 85 85 drum promoted tln/phosphorusloxygen catalysts. 44+2.0 Rb 70 91 85 86 These data indicate that the promoted catalystsimprove conversion, or modivity, or both, in conversion reactionstested.

CATALYST TESTING X Additional catalysts were prepared to further testeffectiveness of the promoted tin/phosphorus/oxygen catalystcompositions. A basic tin/phosphorus/oxygen MCATALYST TESTING X1 TABLEXII 900F., Oxygen 264 GHSV, Feed 300 GHSV Catalyst Conversion Steam No.Catalyst Yield, Modivity, Ratio 0 Na 32.0 29.3 91.7 19.6 46 4 Na 39.037.4 95.9 23.3 47 5 Na 40.0 38.5 96.1 23.3 48 6 Na 41.4 39.5 95.4 21.049 7 Na 35.7 33.2 93.0 19,2 8 Na 24.6 22.8 92.7 23.3 51 9 Na 25.2 22.790.0 20.4 52 1O Na 32.2 29.5 91.8 19.5 53 11 Na 23.8 21.4 90.0 19.3 5412 Na 26.4 22.4 84.8 17.6 13 Na 24.6 21.7 88.5 18.8

TABLE XIII 1000F.. Oxygen 264 GHSV, Feed 300 GHSV Catalyst ConversionSteam No. Catalyst Yield, Modivity, Ratio 45 O Na 38.2 34.4 90,3 19.6 464 Na 46.6 44.2 94.8 23.3 47 5 Na 53.6 50.9 95.0 23.3 48 6 Na 54.0 51.395.0 21.0 49 7 Na 61.4 57.7 93.9 19.2 50 8 Na 44.4 42.0 94.7 23.3 51 9Na 51.2 47.0 91.8 20.4 52 10 Na 56.9 53.1 93.3 19.5 53 11% Na 52.3 47.791.1 19.3 54 12 k Na 53.6 47.5 88.6 17.6 55 13 Nu 50.4 45.7 90.7 18.8

Results obtained are shown below on samples taken after 3 hoursoperation:

sulfate, oxalate, acetate, carbonate, propionate, tartrate, oxide, orhydroxide.

' TABLE xiv 900F., Oxygen 264 GHSV, Feed 300 GHSV Catalyst ConversionSteam No. Catalyst Yield, Modivity, Ratio 56 (S "3 2 .6 25. 3 91.7 i19.6 57 2.5 K 41.4 38.4 92.7 21.1 58 5.0 K 34.0 32.3 95.2 19.3 59 7.5 K33.9 32.3 95.2 19.0 60 10.0 K 24.5 24.1 98.0 19.0 61 12.5 K- 18.8 18.598.2 17.6

TABLE XV 7 1000F., Oxygen 264 GHSV, Feed 300 GHSV Catalyst ConversionSteam No. Catalyst Yield, Modivity, Ratio 56 0.0 K 38.2 34.4 90.3 19.647 2.5 K 45.2 42.2 93.2 21.1 58 5.0 K 47.4 44.2 93.2 19.3 59 7.5 K 46.843.9 93.1 19.0 60 10.0 K 44.7 42.3 94.5 19.0 61 12.5 K 39.7 37.5 94.517.6

These data indicate high effectiveness of our potassium promotedtin/phosphorus/oxygen catalysts.

Reasonable variations and modifications are possible within the scope ofthis disclosure without departing from the spirit and scope thereof.

We claim:

1. A dehydrogenation catalyst composition which consists essentially ofabout 0.1 to 16 weight per cent phosphorus, about to 75 weight per centtin, about 0.1 to 10 weight per cent lithium, wherein said amounts ofphosphorus, tin, and lithium total less than 100 percent such that thedifference therebetween being substantially combined oxygen, all weightpercentages based on total weight of the final said dehydrogenationcatalyst composition.

2. A method of preparing said dehydrogenation catalyst composition asdefined in claim 1 which comprises:

a. admixing at least one phosphorus-containing material and at least onetin-containing material, b. drying said admixed materials from said step(a),

c. adding a lithium metal or lithium-containing mate rial to said driedadmixed materials from step (b),

d. drying said mixed materials from step (c),

e. calcining said dried mixed materials from said step (d), and therebyproducing said dehydrogenation catalyst composition.

3. The process as defined in claim 2 wherein said phosphorus-containingmaterial is an acid, oxide, halide, or a Group la or Ila metal orammonium phosphate;

said tin-containing material is a halide, sulfate, oxide,

nitrate, acetate, or tartrate; and

said lithium-containing material is a nitrate, halide,

4. The process according to claim 3 wherein said drying in said step (d)is conducted for from about 2 to 24 hours at temperatures of from about100 to 300F., and said calcining in said step (e) is conducted for fromabout 1 to 24 hours at temperatures of from about 1,0- 00 to 1,500 F. V

5. An oxidative dehydrogenation process employing the dehydrogenationcatalyst composition as defined in claim 1 wherein is dehydrogenated atleast one material selected from the group consisting of alkenes,cycloalkenes, alkyl-pyridines, and alkyl aromatics, underdehydrogenation conditions including an elevated temperature in thepresence of a molecular oxygencontaining gas.

6. The process according to claim 5 wherein said alkene contains from 3to 10 carbon atoms per molecule,

said cycloalkene contains from 4 to 10 carbon atoms least 2 carbon atomsper said alkyl group;

said dehydrogenation conditions further include a temperature of fromabout 700 to 1,300F., a pressure of from about 0.05 to 250 psia, anoxygen:- gaseous organic compound feed volume ratio of from about 0.121to 3:1, and an organic compound feed space rate of from about 50 to5,000.

7. The process according to claim 6 wherein said oxidativedehydrogenation process further includes the presence of steam, and saidsteam is employed in a volume ratio of steam to organic compound feed offrom about 0.121 to 50:1.

8. The process according to claim 7 wherein said organic compound feedis butene.

9. A method of preparing said dehydrogenation cata- 19 lyst compositionas defined in claim 1 which comprises:

a. admixing at least one phosphorus-containing material and at least onetin-containing material in the form of an aqueous solution or dispersionof said materials containing from about 0.01 to molar 5 concentration ofsaid materials,

b. adding to said aqueous solution or dispersion admixture at least onecompound selected from the group consisting of ammonium hydroxide,sodium hydroxide and potassium hydroxide thereby forming a wet gel,

0. filtering and washing said wet gel,

d. adding lithium metal or a lithium-containing material to said washedgel,

e. drying the resulting composition from step (d),

f. calcining said dried composition from step (e), and thereby producingsaid dehydrogenation catalyst composition.

10. The process according to claim 9 wherein said dehydrogenationcatalyst composition is subjected to a particle forming step prior tothe calcination step.

11. A dehydrogenation catalyst composition which consists essentially ofa calcined composition of about 0.1 to 16 weight per cent phosphorus,about to 75 weight per cent tin, about 0.1 to 10 weight per cent of atleast one Group Ia metal, and oxygen or oxygen and sulfur, all weightpercentages based on total weight of the final said dehydrogenationcatalyst composition.

12. A method of preparing said dehydrogenation catalyst composition asdefined in claim 11 which comprises:

a. admixing at least one phosphorus-containing material and at least onetin-containing material,

b. drying said admixed materials from said step (a),

c. adding a Group Ia metal or Group la metalcontaining material to saiddried admixed materials from step (b),

d. drying said mixed materials from step (c),

e. calcining said dried mixed materials from said step (d), and therebyproducing said dehydrogenation catalyst composition.

13. The process as defined in claim 12 wherein saidphosphorus-containing material is an acid, oxide, halide, or a Group laor lla metal or ammonium phosphate:

said tin-containing material is a halide, sulfate, oxide,

nitrate, acetate, or tartrate; and

said Group la metal-containing material is a nitrate,

halide, sulfate, oxalate, acetate, carbonate, propionate, tartrate,oxide, or hydroxide.

14. The process according to claim 13 wherein said drying in said step(d) is conducted for from about 2 to 24 hours at temperatures of fromabout 100 to 300F., and said calcining in said step (e) is conducted forfrom about 1 to 24 hours at temperatures of from about l,000 to l,500F.

15. The process according to claim 14 wherein said Group la metal ormetal-containing material is at least one of lithium, sodium, orpotassium.

16. An oxidative dehydrogenation process employing the dehydrogenationcatalyst composition as defined in claim 11 wherein is dehydrogenated atleast one material selected from the group consisting of alkenes,cycloalkenes, alkylpyridines, and alkyl aromatics, under dehydrogenationconditions including an elevated temperature in the presence of amolecular oxygencontaining gas.

17. The process according to claim 16 wherein said alkene contains from3 to 10 carbon atoms per molecule, said cycloalkene contains from 4 to10 carbon atoms per molecule, said alkylpyridine and said alkyl aromaticeach contain from 1 to 4 alkyl groups per molecule with at least onesaid alkyl group containing at least 2 carbon atoms per said alkylgroup;

said dehydrogenation conditions further include a temperature of fromabout 700 to 1,300F., apressure of from about 0.05 to 250 psia, anoxygen:- gaseous organic compound feed volume ratio of from about 0.1:1to 3: 1, and an organic compound feed space rate of from about 50 to5,000.

18. The process according to claim 17 wherein said oxidativedehydrogenation process further includes the presence of steam, and saidsteam is employed in a volume ratio of steam to organic compound feed offrom about 0.1:] to 50:1.

19. The process according to claim 18 wherein said at least one Group lametal containing component is lithium, sodium, or potassium.

20. The process according to claim 19 wherein said organic compound feedis butene.

21. A method of preparing said dehydrogenation cat-- alyst compositionas defined in claim 11 which comprises:

a. admixing at least one phosphorus-containing material and at least onetin-containing material in the form of an aqueous solution or dispersionof said materials containing from about 0.01 to 10 molar concentrationof said materials,

b. adding to said aqueous solution or dispersion admixture at least onecompound selected from the group consisting of ammonium hydroxide,sodium hydroxide and potassium hydroxide thereby forming a wet gel,

0. filtering and washing said wet gel,

d. adding an alkali metal or alkali metal containing material to saidwashed gel,

e. drying the resulting composition from step (d),

f. calcining said dried composition from step (e), and thereby producingsaid dehydrogenation catalyst composition.

22. The process according to claim 21 wherein said dehydrogenationcatalyst composition is subjected to a particle forming step prior tothe calcination step.

23. The process according to claim 22 wherein said alkali metal oralkali metal containing material is at least one of lithium, sodium, orpotassium.

2. A method of preparing said dehydrogenation catalyst composition asdefined in claim 1 which comprises: a. admixing at least onephosphorus-containing material and at least one tin-containing material,b. drying said admixed materials from said step (a), c. adding a lithiummetal or lithium-containing material to said dried admixed materialsfrom step (b), d. drying said mixed materials from step (c), e.calcining said dried mixed materials from said step (d), and therebyproducing said dehydrogenation catalyst composition.
 3. The process asdefined in claim 2 wherein said phosphorus-containing material is anacid, oxide, halide, or a Group Ia or IIa metal or ammonium phosphate;said tin-containing material is a halide, sulfate, oxide, nitrate,acetate, or tartrate; and said lithium-containing material is a nitrate,halide, sulfate, oxalate, acetate, carbonate, propionate, tartrate,oxide, or hydroxide.
 4. The process according to claim 3 wherein saiddrying in said step (d) is conducted for from about 2 to 24 hours attemperatures of from about 100* to 300*F., and said calcining in saidstep (e) is conducted for from about 1 to 24 hours at temperatures offrom about 1,000* to 1,500*F.
 5. An oxidative dehydrogenation processemploying the dehydrogenation catalyst composition as defined in claim 1wherein is dehydrogenated at least one material selected from the groupconsisting of alkenes, cycloalkenes, alkyl-pyridines, and alkylaromatics, under dehydrogenation conditions including an elevatedtemperature in the presence of a molecular oxygen-containing gas.
 6. Theprocess according to claim 5 wherein said alkene contains from 3 to 10carbon atoms per molecule, said cycloalkene contains from 4 to 10 carbonatoms per molecule, said alkylpyridine and said alkyl aromatic eachcontain from 1 to 4 alkyl groups per molecule with at least one saidalkyl group containing at least 2 carbon atoms per said alkyl group;said dehydrogenation conditions further include a temperature of fromabout 700* to 1,300*F., a pressure of from about 0.05 to 250 psia, anoxygen:gaseous organic compound feed volume ratio of from about 0.1:1 to3:1, and an organic compound feed space rate of from about 50 to 5,000.7. The process according to claim 6 wherein said oxidativedehydrogenation process further includes the presence of steam, and saidsteam is employed in a volume ratio of steam to organic compound feed offrom about 0.1:1 to 50:1.
 8. The process according to claim 7 wheReinsaid organic compound feed is butene.
 9. A method of preparing saiddehydrogenation catalyst composition as defined in claim 1 whichcomprises: a. admixing at least one phosphorus-containing material andat least one tin-containing material in the form of an aqueous solutionor dispersion of said materials containing from about 0.01 to 10 molarconcentration of said materials, b. adding to said aqueous solution ordispersion admixture at least one compound selected from the groupconsisting of ammonium hydroxide, sodium hydroxide and potassiumhydroxide thereby forming a wet gel, c. filtering and washing said wetgel, d. adding lithium metal or a lithium-containing material to saidwashed gel, e. drying the resulting composition from step (d), f.calcining said dried composition from step (e), and thereby producingsaid dehydrogenation catalyst composition.
 10. The process according toclaim 9 wherein said dehydrogenation catalyst composition is subjectedto a particle forming step prior to the calcination step.
 11. Adehydrogenation catalyst composition which consists essentially of acalcined composition of about 0.1 to 16 weight per cent phosphorus,about 15 to 75 weight per cent tin, about 0.1 to 10 weight per cent ofat least one Group Ia metal, and oxygen or oxygen and sulfur, all weightpercentages based on total weight of the final said dehydrogenationcatalyst composition.
 12. A method of preparing said dehydrogenationcatalyst composition as defined in claim 11 which comprises: a. admixingat least one phosphorus-containing material and at least onetin-containing material, b. drying said admixed materials from said step(a), c. adding a Group Ia metal or Group Ia metal-containing material tosaid dried admixed materials from step (b), d. drying said mixedmaterials from step (c), e. calcining said dried mixed materials fromsaid step (d), and thereby producing said dehydrogenation catalystcomposition.
 13. The process as defined in claim 12 wherein saidphosphorus-containing material is an acid, oxide, halide, or a Group Iaor IIa metal or ammonium phosphate: said tin-containing material is ahalide, sulfate, oxide, nitrate, acetate, or tartrate; and said Group Iametal-containing material is a nitrate, halide, sulfate, oxalate,acetate, carbonate, propionate, tartrate, oxide, or hydroxide.
 14. Theprocess according to claim 13 wherein said drying in said step (d) isconducted for from about 2 to 24 hours at temperatures of from about100* to 300*F., and said calcining in said step (e) is conducted forfrom about 1 to 24 hours at temperatures of from about 1,000* to1,500*F.
 15. The process according to claim 14 wherein said Group Iametal or metal-containing material is at least one of lithium, sodium,or potassium.
 16. An oxidative dehydrogenation process employing thedehydrogenation catalyst composition as defined in claim 11 wherein isdehydrogenated at least one material selected from the group consistingof alkenes, cycloalkenes, alkylpyridines, and alkyl aromatics, underdehydrogenation conditions including an elevated temperature in thepresence of a molecular oxygen-containing gas.
 17. The process accordingto claim 16 wherein said alkene contains from 3 to 10 carbon atoms permolecule, said cycloalkene contains from 4 to 10 carbon atoms permolecule, said alkylpyridine and said alkyl aromatic each contain from 1to 4 alkyl groups per molecule with at least one said alkyl groupcontaining at least 2 carbon atoms per said alkyl group; saiddehydrogenation conditions further include a temperature of from about700* to 1,300*F., a pressure of from about 0.05 to 250 psia, anoxygen:gaseous organic compound feed volume ratio of from about 0.1:1 to3:1, and an organic compound feed space rate of from about 50 to 5,000.18. The process according to claim 17 wherein said oxidativedehydrogenation process further includes the presence of steam, and saidsteam is employed in a volume ratio of steam to organic compound feed offrom about 0.1:1 to 50:1.
 19. The process according to claim 18 whereinsaid at least one Group Ia metal containing component is lithium,sodium, or potassium.
 20. The process according to claim 19 wherein saidorganic compound feed is butene.
 21. A method of preparing saiddehydrogenation catalyst composition as defined in claim 11 whichcomprises: a. admixing at least one phosphorus-containing material andat least one tin-containing material in the form of an aqueous solutionor dispersion of said materials containing from about 0.01 to 10 molarconcentration of said materials, b. adding to said aqueous solution ordispersion admixture at least one compound selected from the groupconsisting of ammonium hydroxide, sodium hydroxide and potassiumhydroxide thereby forming a wet gel, c. filtering and washing said wetgel, d. adding an alkali metal or alkali metal containing material tosaid washed gel, e. drying the resulting composition from step (d), f.calcining said dried composition from step (e), and thereby producingsaid dehydrogenation catalyst composition.
 22. The process according toclaim 21 wherein said dehydrogenation catalyst composition is subjectedto a particle forming step prior to the calcination step.
 23. Theprocess according to claim 22 wherein said alkali metal or alkali metalcontaining material is at least one of lithium, sodium, or potassium.